CN108101111A - A kind of molybdenum carbide/molybdenum dioxide composite nano-line and preparation method and application - Google Patents
A kind of molybdenum carbide/molybdenum dioxide composite nano-line and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of molybdenum carbide/molybdenum dioxide composite nano-lines and preparation method and application.The preparation method, includes the following steps：(1) by the mixing of solution A and solution B, molybdate organic amine hydridization precursor solution is obtained；The solution A is made of molybdate and ethylene glycol；The solution B is made of organic amine substance, ethylene glycol and water；The organic amine substance is any one of melamine, aniline and dicyandiamide or several；(2) under an inert atmosphere, the molybdate organic amine hydridization presoma is pyrolyzed, obtains the molybdenum carbide/molybdenum dioxide composite nano-line.Raw material derives from a wealth of sources, is of low cost, complicated instrument is not required in preparation method building-up process of the present invention, easy to operate, process route is short, controllability is strong, is conducive to large-scale commercial Application；Molybdenum carbide/molybdenum dioxide composite nano-line shows excellent electro-catalysis hydrogen production activity and stability under acidic, neutral and alkaline conditions.
Description
Technical field
The invention belongs to nano material and electro-catalysis hydrogen producing technology field more particularly to a kind of molybdenum carbide/molybdenum dioxide are multiple
Close nano wire and preparation method and application.
Background technology
With the continuous growth to clean energy resource and regenerative resource demand, carrier of the hydrogen as the energy becomes future
The trend of new energy development.Electrolysis water liberation of hydrogen due to its it is environmentally protective and sustainable the advantages that, cause the extensive concern of people.
Since the high cost of noble metal catalyst greatlys restrict the large-scale application of electrolysis water process, exploitation is cheap
And the transistion metal compound being widely present has excellent properties as electrolysis water liberation of hydrogen catalyst particularly under full pH value
Non-precious metal catalyst has extensive prospect and important meaning.
Molybdenum carbide as it is a kind of have fill type compound between metalline, due to carbon enters the lattice of molybdenum and with special
Physical and chemical performance and surface texture, catalytic activity can compare favourably with noble metal platinum, iridium, be referred to as " class platinum catalyst ", be one
The rich promising high-efficient electrolytic water liberation of hydrogen catalyst of class.In addition, in the range of wider pH, the surface of molybdenum carbide forms oxide
The corrosion of electrochemical active material can effectively be inhibited, it is ensured that the stability of evolving hydrogen reaction in the range of its full pH.In recent years, some
Researcher has set about the research of molybdenum carbide elctro-catalyst.(105529474 A of CN) such as Tang's chins or cheeks proposes a kind of graphene package
Super-dispersed nano molybdenum carbide elctro-catalyst, with Mo3(BTC)2Organic framework compounds are obtained after carbonization by 1 as presoma
The catalyst of (1~20 nanometer) composition of super-dispersed nano MoC of~10 layer graphenes package, the equal table under acid and alkaline condition
Reveal high electro-catalysis hydrogen production activity and stability.Zhou Weijia etc. (105731463 A of CN) is with molybdenum ion-resin complexes
Microballoon is presoma, is carbonized under inert atmosphere and obtains molybdenum carbide microballoon.Li Jisen etc. (105562119 A of CN) is to contain molybdenum or tungsten
Heteropoly acid, polymer conductor, graphene be raw material, it is multiple by one pot process heteropoly acid-polymer conductor/reduced graphene
Condensation material, after heat treatment obtains reduced graphene load molybdenum carbide or tungsten catalyst, the structure of catalyst uniqueness greatly limit
The reunion of molybdenum carbide or tungsten nano-particle has been made, has enhanced its dispersiveness.
In recent years, the material with heterojunction structure is attracted wide attention in the application of electrochemical field.Zhang etc.
(Adv.Funct.Mater.2014,24,3399-3404) MoO is prepared by hard template of CMK-33/ CMK-3, nitrogen atmosphere heat at
Molybdenum dioxide/molybdenum carbide nanotube of heterojunction structure is obtained after reason, is shown in terms of lithium ion battery charge and discharge cycles excellent
Performance.Yang etc. (ACS Appl.Mater.Interfaces 2016,8,19987-19993) is using ammonium molybdate and aniline as original
Material, with 1.0M HCl adjust pH=4~5, and when 50 DEG C of constant temperature 2 are small after obtain presoma, dioxy is obtained after high temperature pyrolysis
Change molybdenum/molybdenum carbide/carbon nanocoils, and show excellent charge-discharge performance.Liu et al. (Appl.Surf.Sci.2018,427,
693-701) using ammonium molybdate, beta-cyclodextrin as raw material, through 180 DEG C of hydro-thermals, high temperature pyrolysis obtain the molybdenum dioxide of nucleocapsid/
α-molybdenum carbide shows excellent Hydrogen Evolution Performance, but its preparation process is complicated, and flow is relatively long, affects its commercial Application.
The content of the invention
It, should the object of the present invention is to provide a kind of molybdenum carbide/molybdenum dioxide composite nano-line and preparation method and application
Method simple possible is easy to amplify, the molybdenum carbide/molybdenum dioxide composite nano-line for the heterojunction structure being prepared, due to dioxy
Change electronics synergistic effect and the one-dimentional structure between molybdenum and molybdenum carbide, there is excellent electrolysis water evolving hydrogen reaction performance.
A kind of preparation method of molybdenum carbide/molybdenum dioxide composite nano-line provided by the invention, includes the following steps：
(1) by the mixing of solution A and solution B, molybdate-organic amine hydridization presoma is obtained；The solution A is by molybdate
It is formed with ethylene glycol；The solution B is made of organic amine substance, ethylene glycol and water；The organic amine substance is melamine
Any one of amine, aniline and dicyandiamide are several；
(2) under an inert atmosphere, the molybdate-organic amine hydridization presoma is pyrolyzed, obtain the molybdenum carbide/
Molybdenum dioxide composite nano-line.
Above-mentioned preparation method, in step (1), the volume ratio of the solution A and the solution B can be (5~45)：30,
Concretely 13.5：30.
In the solution A, the ratio of the molybdate and the ethylene glycol can be (0.2~2) g：(10~40) mL, specifically
Can be (0.2~2) g：13.5mL, optimal is 1g：13.5mL.The molybdate is ammonium molybdate, potassium molybdate or sodium molybdate.
In the solution B, the ratio of the organic amine substance, the ethylene glycol and the water can (0.2~2) g：(20
~29.5) mL：(0.5~10) mL, concretely (0.2~2) g：20.7mL：9.3mL, optimal is 1g：20.7mL：9.3mL.
The temperature of the mixing can be 60 DEG C~80 DEG C, concretely 75 DEG C.
The mixing carries out under agitation, and the rotating speed of the stirring is 80~500 revs/min, and concretely 300
Rev/min, the time can be 4~10 it is small when, concretely 2 it is small when.
The method further includes the step of preparing solution A and solution B before the mixing；The temperature of the preparation can be
60 DEG C~80 DEG C, concretely 75 DEG C；The preparation can carry out under agitation, and the speed of the stirring can be 80~300
Rev/min, concretely 180 revs/min；The time of the stirring can be 4~10 it is small when, concretely 8 it is small when.
The method further includes after the mixing separates obtained system, collects solid product；To described
Solid product is washed (as washed successively using acetone and water) and dry step.The drying can be freeze-drying
Or vacuum drying.
Above-mentioned preparation method, in step (2), the temperature of the pyrolysis can be 550 DEG C~900 DEG C, be preferably 600 DEG C~
900 DEG C, more preferably 600 DEG C~800 DEG C, such as 600 DEG C, 650 DEG C, 700 DEG C, 800 DEG C, 900 DEG C；It can be with 1~10 DEG C/min
Heating rate is warming up to the temperature, such as 3 DEG C/min；The time of the pyrolysis can be 1~4 it is small when, concretely 3 it is small when, 2
Hour, 1.5 it is small when, 4 it is small when.
The inert atmosphere is circulation inert gas (such as nitrogen, argon gas), the flow of the inert gas can be 10~
50mL·min-1, concretely 30mLmin-1。
Molybdenum carbide/molybdenum dioxide composite nano-line without free carbon or contains only minute quantity free carbon after the pyrolysis.
The molybdenum carbide being prepared invention further provides above-mentioned preparation method/molybdenum dioxide composite nano-line.
The present invention also provides above-mentioned molybdenum carbide/molybdenum dioxide composite nano-line in following A 1)-A4) in it is any in
Application：
A1) hydrogen manufacturing；
A2) water electrolysis hydrogen production；
A3) the catalyst as water electrolysis hydrogen production；
A4) the electrode material as water electrolysis hydrogen production.
Above-mentioned application is suitable for any one of acid, neutral and alkaline environment, and the molybdenum carbide/molybdenum dioxide is compound
Nano wire shows excellent electro-catalysis hydrogen production activity and stability under acidic, neutral and alkaline conditions.
The present invention has the advantages that：
(1) raw material derives from a wealth of sources, is of low cost, complicated instrument, behaviour is not required in preparation method building-up process of the present invention
Work is simple, process route is short, controllability is strong, is conducive to large-scale commercial Application.
(2) molybdenum carbide of the present invention/molybdenum dioxide composite nano-line is by uniform molybdenum carbide/molybdenum dioxide nano particle group
Into so that the exposure of its active site is more, is conducive to improve its electro catalytic activity, under acidic, neutral and alkaline conditions
Show excellent electro-catalysis hydrogen production activity and stability.
In short, the present invention provides a kind of method that magnanimity prepares molybdenum carbide/molybdenum dioxide heterogeneous structural nano line, the party
Method is simple and practical, and cost of manufacture is relatively low, easy to promote large-scale；Obtained material has good electrochemistry H2-producing capacity, has
It hopes and is applied to water electrolysis hydrogen production field.
Description of the drawings
Fig. 1 is molybdenum carbide/molybdenum dioxide nano wire XRD spectrum that 1-4 of the embodiment of the present invention is prepared.
Molybdenum carbide/molybdenum dioxide nano wire that Fig. 2 is prepared for the embodiment of the present invention 2, the carbon that comparative example 1 is prepared
Change molybdenum nano wire, the Raman collection of illustrative plates for the molybdenum dioxide that comparative example 2 is prepared, in 1350 and 1590cm-1Place shows without peak without certainly
By carbon.
Fig. 3 is the stereoscan photograph of molybdenum carbide/molybdenum dioxide nano wire of 1-4 of the embodiment of the present invention.
Fig. 4 be molybdenum carbide/molybdenum dioxide nano wire transmission electron microscope (a) of the embodiment of the present invention 2, partial enlargement photo (b,
C) and element M apping schemes (d).
Fig. 5 is molybdenum carbide/molybdenum dioxide nano wire of 1-5 of the embodiment of the present invention in 0.5M H2SO4LSV schemes in solution.
Molybdenum carbide/molybdenum dioxide nano wire that Fig. 6 is 1-5 of embodiment of the present invention LSV in 0.1M phosphate buffer solutions schemes.
Molybdenum carbide/molybdenum dioxide nano wire that Fig. 7 is 1-5 of embodiment of the present invention LSV in 1.0M KOH solutions schemes.
Fig. 8 is molybdenum carbide/molybdenum dioxide nano wire of the embodiment of the present invention 2 in 0.5M H2SO4Stability diagram in solution.
Fig. 9 be the embodiment of the present invention 2 molybdenum carbide/molybdenum dioxide nano wire in 0.1M phosphate buffer solutions stability
Figure.
Figure 10 be the embodiment of the present invention 2 molybdenum carbide/molybdenum dioxide nano wire in 1.0M KOH solutions stability diagram.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
It is catalyzed in following embodiments using molybdenum carbide/molybdenum dioxide composite nano-line for being prepared as evolving hydrogen reaction electrode
Agent material, catalytic performance can be characterized with take-off potential and Tafel slope, and under normal circumstances, we use 10mA cm-2Electricity
Overpotential corresponding to current density is as measurement standard.
Embodiment 1 prepares molybdenum carbide/molybdenum dioxide composite nano-line
Molybdenum carbide/molybdenum dioxide composite nano-line is prepared in accordance with the following steps：
(1) ammonium molybdate-melamine presoma is prepared
1g ammonium molybdates and 13.5mL ethylene glycol are weighed in a set of cups, 8h, rotating speed 180 are stirred under 75 DEG C of water bath with thermostatic control
Rev/min, it is denoted as solution A.It weighs 1g melamines and is dissolved in ethylene glycol water mixed solution (ethylene glycol containing 20.7mL and 9.3mL
Water), 8h is stirred under 75 DEG C of waters bath with thermostatic control, rotating speed is 180 revs/min, and acquired solution is denoted as solution B.Treat that solution A, B are cooled to room
Wen Hou mixes solution B and solution A, and mixing stirs 2h after constant temperature at 75 DEG C, and rotating speed is 300 revs/min, terminate it is backward its
Middle addition ethyl alcohol washing, centrifugation, then with acetone are washed for several times, are finally washed with water, it is solid that white is obtained after freeze-drying repeatedly
Body, i.e. ammonium molybdate-melamine presoma.
(2) molybdenum carbide/molybdenum dioxide heterogeneous structural nano line is prepared
Ammonium molybdate-melamine presoma is packed into quartzy Noah's ark, quartzy Noah's ark is pushed into tube furnace central thermal zone position,
And seal up ring flange；By nitrogen after flowmeter (gas flow 30mL min-1) into tube furnace, with 3 DEG C of min-1Heating rate
To 600 DEG C, when constant temperature holding 3 is small；Then, naturally cool to room temperature, take out quartzy Noah's ark to get to molybdenum carbide/molybdenum dioxide
Heterogeneous structural nano line, is denoted as S1.XRD spectra is shown in Fig. 1.Stereoscan photograph is shown in Fig. 3.
Embodiment 2 prepares molybdenum carbide/molybdenum dioxide composite nano-line
Ammonium molybdate obtained in embodiment 1-melamine presoma is packed into quartzy Noah's ark, quartzy Noah's ark is pushed into tubular type
Stove central thermal zone position, and seal up ring flange；By nitrogen after flowmeter (gas flow 30mL min-1) into tube furnace, with 3
℃min-1Heating rate is to 650 DEG C, when constant temperature holding 2 is small；Then, naturally cool to room temperature, take out quartzy Noah's ark to get to carbon
Change molybdenum/molybdenum dioxide heterogeneous structural nano line, be denoted as S2.XRD spectra is shown in Fig. 1.Raman collection of illustrative plates is shown in Fig. 2.Stereoscan photograph is shown in
Fig. 3.Transmission electron microscope, partial enlargement photo and element M apping figures are shown in Fig. 4.
Embodiment 3 prepares molybdenum carbide/molybdenum dioxide composite nano-line
Ammonium molybdate obtained in embodiment 1-melamine presoma is packed into quartzy Noah's ark, quartzy Noah's ark is pushed into tubular type
Stove central thermal zone position, and seal up ring flange；By nitrogen after flowmeter (gas flow 30mL min-1) into tube furnace, with 3
℃min-1Heating rate is to 700 DEG C, when constant temperature holding 1.5 is small；Then, naturally cool to room temperature, take out quartzy Noah's ark to get to
Molybdenum carbide/molybdenum dioxide heterogeneous structural nano line, is denoted as S3.XRD spectra is shown in Fig. 1.Stereoscan photograph is shown in Fig. 3.
Embodiment 4 prepares molybdenum carbide/molybdenum dioxide composite nano-line
Ammonium molybdate obtained in embodiment 1-melamine presoma is packed into quartzy Noah's ark, quartzy Noah's ark is pushed into tubular type
Stove central thermal zone position, and seal up ring flange；By nitrogen after flowmeter (gas flow 30mL min-1) into tube furnace, with 3
℃min-1Heating rate is to 800 DEG C, when constant temperature holding 2 is small；Then, naturally cool to room temperature, take out quartzy Noah's ark to get to carbon
Change molybdenum/molybdenum dioxide heterogeneous structural nano line, be denoted as S4.XRD spectra is shown in Fig. 1.Stereoscan photograph is shown in Fig. 3.
Embodiment 5 prepares molybdenum carbide/molybdenum dioxide composite nano-line
Ammonium molybdate obtained in embodiment 1-melamine presoma is packed into quartzy Noah's ark, quartzy Noah's ark is pushed into tubular type
Stove central thermal zone position, and seal up ring flange；By nitrogen after flowmeter (gas flow 30mL min-1) into tube furnace, with 3
℃min-1Heating rate is to 900 DEG C, when constant temperature holding 4 is small；Then, naturally cool to room temperature, take out quartzy Noah's ark to get to carbon
Change molybdenum/molybdenum dioxide heterogeneous structural nano line, be denoted as S5.
Comparative example 1 prepares molybdenum carbide nano wire
The ammonium molybdate that example 1 is prepared-melamine presoma is packed into quartzy Noah's ark, and quartzy Noah's ark is pushed into tubular type
Stove central thermal zone position, and seal up ring flange；By the gaseous mixture of the argon gas of 10% hydrogen/90% after flowmeter (gas flow
30mL min-1) into tube furnace, with 3 DEG C of min-1Heating rate is to 650 DEG C, when constant temperature holding 2 is small；Then, naturally cool to
Room temperature takes out quartzy Noah's ark to get to molybdenum carbide nano wire, is denoted as D1.Raman collection of illustrative plates is shown in Fig. 2.
Comparative example 2 prepares molybdenum dioxide nano wire
The ammonium molybdate that example 1 is prepared-melamine presoma is packed into quartzy Noah's ark, and quartzy Noah's ark is pushed into tubular type
Stove central thermal zone position, and seal up ring flange；By nitrogen after flowmeter (gas flow 30mL min-1) into tube furnace, with 3
℃min-1Heating rate is to 500 DEG C, when constant temperature holding 2 is small；Then, naturally cool to room temperature, take out quartzy Noah's ark to get to two
Molybdenum oxide nanowires are denoted as D2.Raman collection of illustrative plates is shown in Fig. 2.
Embodiment 6, application
The preparation of working electrode：2mg catalyst samples accurately are weighed, are dissolved in 500 μ L water-ethanols (v/v=4:1) mixed
It closes in solution, adds in 40 μ L (0.5wt%) Nafion solutions, ultrasound 30 minutes obtains uniform black aqueous solution.Take 5 μ L drops
On the glass-carbon electrode polished, it is ensured that card sample substantially uniformity is covered in electrode surface, and working electrode is used as after dry.
Performance test：Pass through Shanghai Chen Hua company CHI-660 type electrochemical workstations, standard three electrode system, platinized platinum/stone
Ink sheet is made to electrode, and saturation calomel (acid condition, neutrallty condition)/Hg/HgO (alkaline condition) is used as reference electrode, will carry
The working electrode for having catalyst is placed in 0.5M H2SO4, 0.1M phosphate buffer solutions, in 1.0M KOH aqueous solutions, using routine
Method carries out liberation of hydrogen linear scan test.
The molybdenum carbide of embodiment 1-5/molybdenum dioxide nano wire is in 0.5M H2SO4Solution, in 0.1M phosphate buffer solutions and
LSV figures are shown in Fig. 5-Fig. 7 in 1.0M KOH solutions.The molybdenum carbide of embodiment 2/molybdenum dioxide nano wire is in 0.5M H2SO4Solution,
Stability diagram in 0.1M phosphate buffer solutions and 1.0M KOH solutions is shown in Fig. 8-Figure 10.Electrocatalysis characteristic test result is summarised in
In Tables 1 and 2.
Electrocatalysis characteristic test result in 1 acid medium of table
Electrocatalysis characteristic test result in 2 neutrality of table and alkaline medium
1-10, the experimental result of Tables 1 and 2 understand that there is prepared material molybdenum carbide/molybdenum dioxide to receive with reference to the accompanying drawings
Nanowire structure improves the electric conductivity of catalyst, shows excellent electrolysis water liberation of hydrogen under acidic, neutral and alkaline conditions
Performance and stability.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from the embodiment
Limitation, such as the melamine of the present invention can also be aniline, dicyandiamide；Molybdate can be with potassium molybdate or sodium molybdate other molybdic acids
Salt；Other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of molybdenum carbide/molybdenum dioxide composite nano-line, includes the following steps：
(1) by the mixing of solution A and solution B, molybdate-organic amine hydridization precursor solution is obtained；The solution A is by molybdate
It is formed with ethylene glycol；The solution B is made of organic amine substance, ethylene glycol and water；The organic amine substance is melamine
Any one of amine, aniline and dicyandiamide are several；
(2) under an inert atmosphere, the molybdate-organic amine hydridization presoma is pyrolyzed, obtains the molybdenum carbide/dioxy
Change molybdenum composite nano-line.
2. preparation method according to claim 1, it is characterised in that：In step (1), the solution A and the solution B
Volume ratio is (5~45)：30；
In the solution A, the ratio of the molybdate and the ethylene glycol is (0.2~2) g：(10~40) mL；The molybdate
For ammonium molybdate, potassium molybdate or sodium molybdate；
In the solution B, the ratio of the organic amine substance, the ethylene glycol and the water is (0.2~2) g：(20~
29.5)mL：(0.5~10) mL.
3. preparation method according to claim 1 or 2, it is characterised in that：In step (1), the temperature of the mixing is 60
DEG C~80 DEG C.
4. preparation method according to any one of claim 1-3, it is characterised in that：In step (1), described be blended in is stirred
It is carried out under the conditions of mixing, the rotating speed of the stirring is 80~500 revs/min, when the time of the stirring is 4~10 small.
5. according to the preparation method any one of claim 1-4, it is characterised in that：In step (1), the method is in institute
It states to further include after mixing and obtained system is separated, collect solid product；The solid product is washed and done
Dry step.
6. according to the preparation method any one of claim 1-5, it is characterised in that：In step (2), the temperature of the pyrolysis
It spends for 550 DEG C~900 DEG C, when the time is 1~4 small.
7. preparation method according to claim 6, it is characterised in that：Institute is warming up to 1~10 DEG C/min of heating rate
State temperature.
8. according to the preparation method any one of claim 1-7, it is characterised in that：In step (2), the inert atmosphere
For the inert gas that circulates, the flow of the inert gas is 10~50mLmi n-1。
9. the molybdenum carbide that the preparation method any one of claim 1-8 is prepared/molybdenum dioxide composite nano-line.
10. molybdenum carbide/molybdenum dioxide composite nano-line described in claim 9 is in following A 1)-A4) in it is any in application：
A1) hydrogen manufacturing；
A2) water electrolysis hydrogen production；
A3) the catalyst as water electrolysis hydrogen production；
A4) the electrode material as water electrolysis hydrogen production.
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